Lithium Ion Coupled Electron-Transfer Rates in Superconcentrated Electrolytes: Exploring the Bottlenecks for Fast Charge-Transfer Rates with LiMn2O4 Cathode Materials

The charge-transfer kinetics of lithium ion intercalation into LixMn2O4 cathode materials was examined in dilute and concentrated aqueous and carbonate LiTFSI solutions using electrochemical methods. Distinctive trends in ion intercalation rates were observed between water-based and ethylene carbonate/diethyl carbonate solutions. The influence of the solution concentration on the rate of lithium ion transfer in aqueous media can be tentatively attributed to the process associated with Mn dissolution, whereas in carbonate solutions the rate is influenced by the formation of a concentration-dependent solid electrolyte interface (SEI). Some indications of SEI layer formation at electrode surfaces in carbonate solutions after cycling are detected by X-ray photoelectron spectroscopy. The general consequences related to the application of superconcentrated electrolytes for use in advanced energy storage cathodes are outlined and discussed.